US4515903A - Cracking catalyst - Google Patents
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- US4515903A US4515903A US06/581,272 US58127284A US4515903A US 4515903 A US4515903 A US 4515903A US 58127284 A US58127284 A US 58127284A US 4515903 A US4515903 A US 4515903A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 178
- 238000005336 cracking Methods 0.000 title claims abstract description 63
- 239000002245 particle Substances 0.000 claims abstract description 104
- 239000010457 zeolite Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 25
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 20
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 206010027439 Metal poisoning Diseases 0.000 claims abstract description 11
- 239000011159 matrix material Substances 0.000 claims abstract description 9
- 229910018404 Al2 O3 Inorganic materials 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 6
- 229910052815 sulfur oxide Inorganic materials 0.000 claims description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- 238000009826 distribution Methods 0.000 claims description 4
- 238000005243 fluidization Methods 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 28
- 230000000694 effects Effects 0.000 abstract description 26
- 229910052751 metal Inorganic materials 0.000 description 27
- 239000002184 metal Substances 0.000 description 27
- 238000011109 contamination Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- 239000000292 calcium oxide Substances 0.000 description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- 239000000571 coke Substances 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 5
- -1 rare earth metal chlorides Chemical class 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 229910000323 aluminium silicate Inorganic materials 0.000 description 4
- 229910052681 coesite Inorganic materials 0.000 description 4
- 229910052906 cristobalite Inorganic materials 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 229910052682 stishovite Inorganic materials 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 229910052905 tridymite Inorganic materials 0.000 description 4
- 229910052720 vanadium Inorganic materials 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000011362 coarse particle Substances 0.000 description 3
- 239000000356 contaminant Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 2
- 235000011128 aluminium sulphate Nutrition 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical group [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000011284 combination treatment Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/084—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S502/00—Catalyst, solid sorbent, or support therefor: product or process of making
- Y10S502/521—Metal contaminant passivation
Definitions
- a fluidized catalyst bed is often employed in the cracking of hydrocarbons.
- the hydrocarbons are fed through the bed in order to be brought into contact with the catalyst particles in the catalyst bed.
- the catalyst is particulate having a particle size and particle size distribution suitable for the contemplated purpose and for the fluidization.
- the catalyst contains zeolite material which is combined with material which is relatively less active or inactive as regards a cracking catalyst effect
- zeolite material which is combined with material which is relatively less active or inactive as regards a cracking catalyst effect
- prior art catalysts are often prepared by intermixing silica, kaolin, sulfuric acid, aluminum salt and previously prepared NaY-zeolite to a mixture which is spray-dried, washed with water, ion-exchanged with ammonium sulfate, washed with water ion-exchanged with rare earth metal chlorides, washed with water, dried and finally calcined.
- a vital problem involved in the use of catalysts for cracking in a fluidized bed is the metal contamination or poisoning to which the catalyst is exposed since this contamination entails reduced product yield (gasoline) and increased production of coke and gas and can, therefore, require replacement of the catalyst.
- One object of the present invention is, therefore, to improve the ability of prior art catalysts to resist metal contamination.
- a further object is to provide a novel cracking catalyst which is heterogeneous and is selective for the production of gasoline.
- the cracking catalyst according to the invention comprises particle fractions of different particle size and different chemical composition, the cracking catalyst component constituting the coarser particle size fractions, and at least the major portion of the material which is relatively less active or inactive in cracking catalyzing respect being of finer particle size fractions.
- the attached drawing is a diagram showing test results obtained in Example 4 below.
- the cracking catalyst according to the invention displays a good level of resistance to metal contamination or poisoning as a result of the fact that the cracking catalyst is formed from at least two particle fractions of different particle size ranges, the zeolite material acting as cracking catalyst being concentrated to the coarser particle size fractions, and the finer particle size fractions being formed from a material which is relatively less active in cracking catalyzing respect or has no or insignificant cracking catalyzing activity.
- the particles of the fine particle size fractions have a matrix of kaolin and amorphous aluminasilica or aluminosilicate and can, in preferred embodiments of the invention, contain, for example, SO x eliminating or picking-up additives such as one or more oxides of calcium, aluminum and magnesium.
- the coarser particle size fractions having a cracking catalyzing effect have a mean particle size of from 80 to 125, preferably from 80 to 100 ⁇ m, and the finer particle size fractions a mean particle size of from 30 to 75, preferably from 30 to 60 ⁇ m.
- the relative proportions of coarser to finer particle size fractions are such that the catalyst as a whole will have a particle size distribution which is suitable for fluidizing purposes.
- the relative contents of the coarser and finer particle size fractions have also been selected for attaining a total content of zeolite material in the catalyst which is suitable for the cracking process.
- the particles of the coarser particle size fraction preferably have a zeolite content of at least 20 weight% and up towards 100 weight%, the remainder consisting of material which is relatively less active in cracking catalyzing respect or has no or insignificant cracking catalyzing activity and may consist of kaolin and amorphous alumina silica or aluminosilicate.
- the catalyst may have a total zeolite content of up to 50 weight%.
- U.S. Pat. No. 2,651,600 discloses a method of reducing contaminants on a finely divided catalyst having a homogeneous composition, in which method the finer fractions of the catalyst are continuously removed from the reactor to remove the catalyst particles having the highest degree of metal poisoning.
- the U.S. patent does not disclose the present invention according to which the catalyst material having the highest cracking catalyzing activity should be concentrated in the coarser particle fractions of the catalyst while the finer particle fractions are formed from a material being relatively less active or having no or insignificant activity in cracking catalyzing respect.
- U.S. Pat. No. 3,597,349 discloses a two-component catalyst containing discrete particles of two different catalyst materials having high catalyzing activity, one component comprising an ultrastable, large-pore crystalline alumino-silicate material in a matrix of an amorphous silica-alumina and metals of groups VI-A and VIII of the Periodic Table of elements, and the other component comprising cation-exchanged Y-type molecular sieves.
- Printed UK patent specification GB No. 2,023,639-A discloses a cracking catalyst having two different types of catalyst material having different particle sizes to enable a separation of the different types of catalyst material after use of the catalyst.
- This prior art specification does not disclose the present invention, i.e. that the catalyst material of higher cracking activity should be concentrated to the coarser particle fractions. Neither does it describe or suggest that metal poisoning problems in cracking catalysts may be reduced by such a distribution of materials in the catalyst mass.
- the coarser particle size fractions have a higher content of zeolite material in order to compensate for the absence of zeolite material in the finer particle size fractions.
- the relative metal contamination resistance capacity is believed to be equal to the relationship between volume and specific surface area of the coarser particle size fractions and of the normal, prior art catalysts for cracking in a fluidized bed.
- the higher zeolite content in the thin jacket which is created close to the surface of the particles of the coarse particle size fraction where the metals are entrapped allows for the entrapment of more metal than is the case in prior art catalysts. This would consequently increase the resistance capacity of the present catalyst to metal contamination.
- This improved resistance capacity to metal contamination in the catalyst according to the present invention as compared with prior art catalysts for fluidized bed cracking is thus believed to depend upon a physical factor, namely the larger particle size of the active catalyst particles, and a chemical-physical factor, that is to say the higher zeolite content in these coarse, catalytically active particles.
- the coarser fractions and finer fractions have substantially the same abrasion resistance capacity because the matrix in the discrete particles is the same in both cases, namely kaolin and amorphous alumina-silica or aluminosilicate, there having been added zeolite material to the matrix of the particles in the coarser particle size fractions and possibly an SO x eliminating or picking-up additive (for example Al 2 O 3 , CaO and MgO) to the matrix of the particles in the finer particle size fractions.
- the finer particle size fractions may also be impregnated with other chemical substances for particular functions, for example platinum or palladium for complete CO combustion.
- Examples 1 and 2 relate to preliminary tests for illustrating the different capacities of coarse and fine paticle size fractions to withstand metal contamination or poisoning.
- a conventional cracking catalyst for cracking of hydrocarbons in a fluidized catalyst bed was prepared by the following steps: silica, kaolin, sulfuric acid, aluminum sulfate and a previously prepared zeolite NaY were intermixed, spray-dried, washed with water, ion-exchanged with ammonium ions, washed with water, ion-exchanged with rare earth metal ions, washed with water, dried and calcined.
- the relative proportions and treatment steps were such that the fresh catalyst had the following composition and properties:
- This catalyst was used for cracking a gas oil in a commercial cracker.
- the density of the gas oil employed was 0.920 g/cm 3 , its 50% boiling point was 389° C., its sulfur content was 1.43% and its metal index was 7.0%.
- the catalyst was utilized for more than a month for cracking under normal cracking conditions, the conversion being 62%, the weight ratio of catalyst to oil was 6.6:1 and the temperature was 495° C. in the reactor of the cracker.
- the coarser fraction has a higher resistance to metal contamination than the finer fraction at identical conversion conditions.
- the selectivity of the fresh catalyst for gasoline production was investigated by a Micro Activity Test (MAT) according to the ASTM Subcommitte D-32.04, the following result being obtained after water vapor treatment in 100% vapor at 750° C. for different periods of time.
- MAT Micro Activity Test
- the two catalyst fractions were also subjected to MAT examination separately, that is to say these catalyst fractions had previously been on stream for more than a month.
- the result of the MAT examination with the two fractions was as follows:
- Example 1 was repeated with a further batch of the same catalyst, this batch being run at more severe cracking conditions.
- the gas oil of Example 2 had a density of 0.915 g/cm 3 , a 50% boiling point of 392° C., a sulfur content of 1.96 weight% and a metal index of 9.6.
- the conversion was 64%
- the weight ratio of catalyst to oil was 6.6:1
- the temperature was 495° C. in the reactor of the cracker.
- the catalyst was divided into two fractions in accordance with Example 1, whereafter the coarser and finer fractions were analysed for their Ni and V contents. The analysis results were as follows:
- a catalyst material was prepared which contained from 25 to 30% zeolite Y, the remainder being amorphous alumina-silica and kaolin. From the obtained catalyst material, particles which was smaller than 80 ⁇ m and larger than 100 ⁇ m were separated by screening. The remaining particles which were in the size range of from 80 to 100 ⁇ m and which were to form the coarse fraction of the contemplated catalyst were then subjected to careful ion exchange first with ammonium ions and subsequently with rare earth metal ions. The final product was carefully washed with water and dried.
- a fine particulate fraction which contained from 25 to 35% CaO.
- the preparation of this fraction was carried out by adding CaO powder to a slurry of kaolin and amorphous alumina-silica (the same as was utilized in the preparation of the coarse fraction), followed by spray drying of the mixture in a small spray drier. Particles which were smaller than 30 ⁇ m and larger than 60 ⁇ m were removed from this spray-dried product by screening. An amount of 15 kg of the thus obtained powder was mixed with 15 kg of the coarse fraction prepared in accordance with the above so as to form a catalyst.
- the thus prepared catalyst with coarse particles of high cracking activity and fine particles of relatively lower cracking activity had the composition illustrated under col. II in Table 1.
- a further coarse-particulate catalyst component was prepared in the manner disclosed above for coarse fractions, and thereafter a fine-particulate catalyst component was prepared having the above-disclosed composition with the exception that the calcium oxide was replaced by aluminum oxide. These two fractions were intermixed to form a catalyst in which the most cracking-active material was concentrated to the coarse-particulate fraction. The analysis of the finished catalyst is apparent from col. I in Table 1.
- catalyst II and the standard catalyst i.e. the catalyst according to Example 1 prior to division into a coarse and a fine fraction
- vapour treatment with 100% water vapor at a temperature of 750° C. for 3 hours, 18 hours and 42 hours, respectively, for three different catalyst batches.
- the treated catalyst samples were subjected to MAT examination. In this examination, the following results were obtained.
- catalyst II behaves substantially in the same manner as the standard catalyst as regards cracking capacity and resistance to aging.
- catalyst II and the standard catalyst were subjected to an abrasion resistance test in which high velocity air jets were blown for 3 hours at room temperature through a catalyst batch enclosed in a tube, and during which particles finer than 20 ⁇ m were permitted to escape to investigate the weight reduction as a result of attrition to the batch.
- catalyst II sustained a weight loss of 0.43 weight%/hour on average
- the standard catalyst sustained a weight loss of 0.4 weight%/hour on average.
- the attrition resistance of the two catalysts was essentially the same.
- a catalyst material was prepared containing about 36 %wt zeolite RE-Y, the remainder being amorphous alumina-silica and kaolin.
- the spray-drying was carried out in such a way that the mean particle size of the obtained catalyst material became about 125 ⁇ m and the particle size range from about 80 to about 160 ⁇ m. This catalyst material was then used as a coarse particulate fraction in producing a catalyst (A) according to the invention.
- the same method was used for producing a fine particulate fraction having a mean particle size of about 45 ⁇ m and a particle size range of from 20 to about 80 ⁇ m. In this case, however, the zeolite NaY was omitted. This fine particulate fraction contained 62.5 %wt SiO 2 and 37.5 %wt Al 2 O 3 .
- the attrition resistance of the two catalyst fractions was found to be 0.33 %wt/h on average for the coarse and 0.36 %wt/h on average for the fine particulate fraction, measured as disclosed in Example 3.
- the coarse and fine particulate catalyst fractions thus prepared were mixed in weight proportions 1:1 so that the mixed catalyst (A) contained in total 62.15 %wt SiO 2 , 34.7 %wt Al 2 O 3 and 3.15 %wt RE 2 O 3 , the average content of zeolite RE-Y in the catalyst mass being about 18 %wt.
- a comparison catalyst B was prepared containing about 18 %wt zeolite RE-Y, the remainder being amorphous alumina-silica and kaolin.
- This catalyst material contained about 3.3 %wt RE 2 O 3 , about 62 %wt SiO 2 and about 34.7 %wt Al 2 O 3 .
- the spray-drying was carried out in such a way that the mean particle size became about 65 ⁇ m and the particle size range from about 20 to about 150 ⁇ m.
- the catalysts A and B thus prepared were then used as catalysts in a fluid catalytic cracker which was a pilot plant cracker and was charged with 35 g catalyst.
- Each catalyst was first steam treated in 100% steam at a pressure of about 100 kPa and a temperature of 750° C. during 5 h for aging the catalyst before using it in the reactor of the cracker for repeated cracking and regeneration cycles.
- the feedstock preheated to 60° C. was fed to the reactor to be distributed throughout the fluidized catalyst bed at the bottom section of the reactor.
- the reactor was on stream for about 5 minutes to crack the feedstock under the reaction cycle conditions:
- the used catalyst was stripped with nitrogen and the reactor temperature was increased to the regeneration temperature 710° C.
- the regeneration was performed by blowing air through the catalyst for 30 minutes.
- the catalyst being thus freed from carbon deposits was then cooled in the reactor to the normal cracking temperature 482° C., the cycle being then repeated.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Glass Compositions (AREA)
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
SE8004825 | 1980-06-30 | ||
SE8004825A SE438449B (sv) | 1980-06-30 | 1980-06-30 | Krackningskatalysator for krackning av kolveten i en med fluidiserad katalysatorbedd arbetande reaktor |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06349087 Continuation | 1982-02-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
US4515903A true US4515903A (en) | 1985-05-07 |
Family
ID=20341330
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US06/581,272 Expired - Fee Related US4515903A (en) | 1980-06-30 | 1984-02-17 | Cracking catalyst |
Country Status (13)
Country | Link |
---|---|
US (1) | US4515903A (sv) |
EP (1) | EP0043358B1 (sv) |
JP (1) | JPS6344011B2 (sv) |
AT (1) | ATE11425T1 (sv) |
AU (1) | AU545095B2 (sv) |
BR (1) | BR8108657A (sv) |
CA (1) | CA1165301A (sv) |
DE (1) | DE3168458D1 (sv) |
FI (1) | FI69409C (sv) |
NO (1) | NO151883C (sv) |
RO (1) | RO84775B (sv) |
SE (1) | SE438449B (sv) |
WO (1) | WO1982000105A1 (sv) |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4781816A (en) * | 1987-10-19 | 1988-11-01 | Phillips Petroleum Company | Cracking process |
US4789654A (en) * | 1985-03-29 | 1988-12-06 | Catalysts & Chemicals Industries Co., Ltd. | Hydrotreating catalysts |
US4944865A (en) * | 1982-05-06 | 1990-07-31 | Chevron Research Company | Process for cracking high metals content feedstocks |
US5059302A (en) * | 1989-05-16 | 1991-10-22 | Engelhard Corporation | Method and apparatus for the fluid catalytic cracking of hydrocarbon feed employing a separable mixture of catalyst and sorbent particles |
US5126298A (en) * | 1991-03-12 | 1992-06-30 | Mobil Oil Corp. | Cracking catalysts comprising clays with different particle sizes, and method of preparing and using the same |
US5141624A (en) * | 1989-03-30 | 1992-08-25 | Phillips Petroleum Company | Catalytic cracking process |
US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
US5413978A (en) * | 1993-11-30 | 1995-05-09 | Engelhard Corporation | Catalytically inert particles for blending with petroleum cracking catalyst |
US5439860A (en) * | 1992-04-16 | 1995-08-08 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks |
US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
US20110079543A1 (en) * | 2009-10-02 | 2011-04-07 | Mitchell James Willis | Heavy Metals Trapping Co-Catalyst For FCC Processes |
US20110132808A1 (en) * | 2011-01-12 | 2011-06-09 | Basf Corporation | Rare Earth-Containing Attrition Resistant Vanadium Trap for Catalytic Cracking Catalyst |
WO2019094603A1 (en) | 2017-11-10 | 2019-05-16 | Basf Corporation | A metal trap for use in fluid catalytic cracking (fcc) |
WO2019118815A1 (en) | 2017-12-15 | 2019-06-20 | Basf Corporation | Vanadium traps for catalytic cracking processes |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS57196720A (en) * | 1981-05-28 | 1982-12-02 | Toyo Soda Mfg Co Ltd | Molded body of modified zeolite |
GB2138314B (en) * | 1983-04-21 | 1987-07-22 | Grace W R & Co | Catalytic cracking catalyst and process |
US4918036A (en) * | 1984-08-16 | 1990-04-17 | W. R. Grace & Co.-Conn. | Cracking catalyst/sulfur oxide gettering agent compositions |
EP0176150B2 (en) * | 1984-09-25 | 1994-02-02 | Catalysts & Chemicals Industries Co., Ltd. | Catalytic cracking, process for heavy oil |
EP0189267A3 (en) * | 1985-01-14 | 1987-06-10 | Engelhard Corporation | Fluidizable composition for catalytic cracking |
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US2651600A (en) * | 1950-02-21 | 1953-09-08 | Standard Oil Dev Co | Method of reducing contaminants on finely divided catalyst |
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US4240899A (en) * | 1979-11-05 | 1980-12-23 | Exxon Research & Engineering Co. | Sulfur transfer process in catalytic cracking |
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US3758403A (en) * | 1970-10-06 | 1973-09-11 | Mobil Oil | Olites catalytic cracking of hydrocarbons with mixture of zsm-5 and other ze |
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US4032432A (en) * | 1975-08-28 | 1977-06-28 | Mobil Oil Corporation | Conversions of hydrocarbons |
SE389666B (sv) * | 1975-09-30 | 1976-11-15 | Mobil Oil Corp | Forfarande for framstellning av kolveten ur syntetgas i kontakt med en katalysator som innefattar en metall eller metallforening samt ett kristallint aluminiumsilikat |
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US4146463A (en) * | 1976-10-12 | 1979-03-27 | Standard Oil Company (Indiana) | Removal of carbon monoxide and sulfur oxides from refinery flue gases |
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US4116814A (en) * | 1977-07-18 | 1978-09-26 | Mobil Oil Corporation | Method and system for effecting catalytic cracking of high boiling hydrocarbons with fluid conversion catalysts |
CA1092082A (en) * | 1977-10-27 | 1980-12-23 | John Mooi | Catalyst and process for conversion of hydrocarbons |
CA1154735A (en) * | 1978-09-11 | 1983-10-04 | Stanley M. Brown | Catalytic cracking with reduced emissions of sulfur oxides |
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1980
- 1980-06-30 SE SE8004825A patent/SE438449B/sv not_active IP Right Cessation
-
1981
- 1981-06-24 DE DE8181850115T patent/DE3168458D1/de not_active Expired
- 1981-06-24 AT AT81850115T patent/ATE11425T1/de not_active IP Right Cessation
- 1981-06-24 BR BR8108657A patent/BR8108657A/pt not_active IP Right Cessation
- 1981-06-24 JP JP56502247A patent/JPS6344011B2/ja not_active Expired
- 1981-06-24 AU AU73703/81A patent/AU545095B2/en not_active Ceased
- 1981-06-24 EP EP81850115A patent/EP0043358B1/en not_active Expired
- 1981-06-24 WO PCT/SE1981/000185 patent/WO1982000105A1/en active IP Right Grant
- 1981-06-29 CA CA000380854A patent/CA1165301A/en not_active Expired
-
1982
- 1982-02-25 FI FI820658A patent/FI69409C/fi not_active IP Right Cessation
- 1982-02-26 RO RO106749A patent/RO84775B/ro unknown
- 1982-02-26 NO NO820614A patent/NO151883C/no unknown
-
1984
- 1984-02-17 US US06/581,272 patent/US4515903A/en not_active Expired - Fee Related
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US2651600A (en) * | 1950-02-21 | 1953-09-08 | Standard Oil Dev Co | Method of reducing contaminants on finely divided catalyst |
US4151121A (en) * | 1976-04-12 | 1979-04-24 | Exxon Research & Engineering Co. | Hydrocarbon conversion catalyst containing a co-oxidation promoter |
US4285806A (en) * | 1978-03-24 | 1981-08-25 | Atlantic Richfield Company | Catalyst and process for conversion of hydrocarbons |
US4240899A (en) * | 1979-11-05 | 1980-12-23 | Exxon Research & Engineering Co. | Sulfur transfer process in catalytic cracking |
US4442223A (en) * | 1979-12-17 | 1984-04-10 | Mobil Oil Corporation | Catalyst and catalyst support compositions |
US4325811A (en) * | 1980-12-08 | 1982-04-20 | Standard Oil Company (Indiana) | Catalytic cracking with reduced emission of noxious gas |
US4465779A (en) * | 1982-05-06 | 1984-08-14 | Gulf Research & Development Company | Modified cracking catalyst composition |
Cited By (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4944865A (en) * | 1982-05-06 | 1990-07-31 | Chevron Research Company | Process for cracking high metals content feedstocks |
US4789654A (en) * | 1985-03-29 | 1988-12-06 | Catalysts & Chemicals Industries Co., Ltd. | Hydrotreating catalysts |
US4781816A (en) * | 1987-10-19 | 1988-11-01 | Phillips Petroleum Company | Cracking process |
US5141624A (en) * | 1989-03-30 | 1992-08-25 | Phillips Petroleum Company | Catalytic cracking process |
US5059302A (en) * | 1989-05-16 | 1991-10-22 | Engelhard Corporation | Method and apparatus for the fluid catalytic cracking of hydrocarbon feed employing a separable mixture of catalyst and sorbent particles |
US5126298A (en) * | 1991-03-12 | 1992-06-30 | Mobil Oil Corp. | Cracking catalysts comprising clays with different particle sizes, and method of preparing and using the same |
US5439860A (en) * | 1992-04-16 | 1995-08-08 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks |
US5593570A (en) * | 1992-04-16 | 1997-01-14 | Chevron Research And Technology Company, A Division Of Chevron U.S.A. Inc. | Catalyst system for combined hydrotreating and hydrocracking and a process for upgrading hydrocarbonaceous feedstocks |
US5384041A (en) * | 1992-12-08 | 1995-01-24 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
US5300469A (en) * | 1992-12-08 | 1994-04-05 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
CN1043966C (zh) * | 1992-12-08 | 1999-07-07 | 恩格尔哈德公司 | 用于催化裂化中钝化钒的组合物及其制备方法 |
WO1994013755A1 (en) * | 1992-12-08 | 1994-06-23 | Engelhard Corporation | Composition for passivating vanadium in catalytic cracking and preparation thereof |
US5413978A (en) * | 1993-11-30 | 1995-05-09 | Engelhard Corporation | Catalytically inert particles for blending with petroleum cracking catalyst |
US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
US8372269B2 (en) | 2009-10-02 | 2013-02-12 | Basf Corporation | Heavy metals trapping co-catalyst for FCC processes |
US20110079543A1 (en) * | 2009-10-02 | 2011-04-07 | Mitchell James Willis | Heavy Metals Trapping Co-Catalyst For FCC Processes |
US20110132808A1 (en) * | 2011-01-12 | 2011-06-09 | Basf Corporation | Rare Earth-Containing Attrition Resistant Vanadium Trap for Catalytic Cracking Catalyst |
US9029291B2 (en) | 2011-01-12 | 2015-05-12 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
US9637688B2 (en) | 2011-01-12 | 2017-05-02 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
US10066170B2 (en) | 2011-01-12 | 2018-09-04 | Basf Corporation | Rare earth-containing attrition resistant vanadium trap for catalytic cracking catalyst |
WO2019094603A1 (en) | 2017-11-10 | 2019-05-16 | Basf Corporation | A metal trap for use in fluid catalytic cracking (fcc) |
US11498054B2 (en) | 2017-11-10 | 2022-11-15 | Basf Corporation | Metal trap for use in fluid catalytic cracking (FCC) |
WO2019118815A1 (en) | 2017-12-15 | 2019-06-20 | Basf Corporation | Vanadium traps for catalytic cracking processes |
Also Published As
Publication number | Publication date |
---|---|
SE8004825L (sv) | 1981-12-31 |
FI69409B (fi) | 1985-10-31 |
JPS6344011B2 (sv) | 1988-09-02 |
CA1165301A (en) | 1984-04-10 |
NO151883C (no) | 1985-06-26 |
ATE11425T1 (de) | 1985-02-15 |
RO84775A (ro) | 1984-11-25 |
RO84775B (ro) | 1984-11-30 |
BR8108657A (pt) | 1982-05-11 |
EP0043358B1 (en) | 1985-01-23 |
JPS57501018A (sv) | 1982-06-10 |
NO151883B (no) | 1985-03-18 |
FI69409C (fi) | 1986-02-10 |
NO820614L (no) | 1982-02-26 |
AU545095B2 (en) | 1985-06-27 |
AU7370381A (en) | 1982-02-02 |
WO1982000105A1 (en) | 1982-01-21 |
EP0043358A1 (en) | 1982-01-06 |
DE3168458D1 (en) | 1985-03-07 |
FI820658L (fi) | 1982-02-25 |
SE438449B (sv) | 1985-04-22 |
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